Lubricants



Patented Jan. 16, 1945 LUBRICANTS Lawson W. Mixon and Clarence M. Loane, Ham

mond, Ind., assignors to Standard Oil Company, Chicago, 111., a corporation of Indiana No Drawing. Application August 15, 1942, Serial No. 454,975

13 Claims.

The present invention relates to lubricants, and particularly to improvements in lubricating oil compositions intended for use in internal combustion engines such as automobile and Diesel engines, under severe conditions, wherein corrosion due to acidity. piston ring sticking, cylinder wear, carbon sludge. varnish formation and viscosity increase may be encountered.

Straight petroleum lubricants are efiective within certain defined limits of engine operating conditions but when these limits are exceeded, such lubricants frequently fail to give the desired performance demanded of them. Since in modern engines designed to give increased performance these limits are frequently exceeded, the use of straight mineral oils as lubricants produces undesirable conditions within the engine; thus varnish, carbon and sludge formation is excessive and corroson of improved hard metal alloy bearings due to acidity is encountered.

It is an object of the present invention to provide a lubricant for internal combustion engines which will be effective in providing adequate inbricat'nn for such engines. It is a further object of the invention to provide a lubricant which will not be inducive to the formation of varnish and/r sludge, nor ind-ucive to an increase of viscosity. Another object of the invention is to prov'de a lubricant Which will reduce engine wear and be non-corrosive to bearings. Other objects and advantages of the invention will become apparent as the description thereof proceeds.

We have discovered that the forego'ng objects may be attained by employing a lubricating oil containing small amounts of the reaction product of a hydrocarbon or mixture thereof with chlorosulfonic acirl. If desired, the reaction product may be neutralized by forming the metal salts thereof. Furthermore, the reaction product may be reacted with a sulfur and/or a phosphcruscontaining compound, either before or after ncutralization. Also, the hydrocarbon may be treated with the sulfur and/or phosphorus-contaningv particularly suitable. These hydrocarbons may be heavy oils, olefin polymers, parafiins, olefins, aromatics, alkylated aromatics, cyclic aliphatics, petroleum fractions, such as lubricating oil fractions, waxes, petrolatum, solvent extracts of petroleum fractions, cracked cycle stocks or condensation products of petroleum fractions, or the like. Aliphatic compounds are usually preferred over the aromatic compounds.

Essentially saturated hydrocarbons such as bright stock residuums, lubricating oil distillates, petrolatums, or parafiln waxes maybe used. We may also employ the products resulting from the condensation of any of the foregoing hydrocarbons, usually thru first halogenating the hydrocarbons, with aromatic hydrocarbons in the presence of anhydrous inorganic halides, such as aluminum chloride, zinc chloride, boron fluoride and the like.

We preferably-employ olefin polymers having molecularweights above and preferably between 500 and 3000. As olefinlc starting materials for the productionof such polymers, we may employ the individual olefins themselves, mixtures of olefins, or mixtures of olefins and non-olefinic compounds. For example, the olefinic starting material maybe propylene, butylene, amylenes, refinery gases containing normally gaseous olefins and cracked distillates or other relatively low-boiling hydrocarbon mixtures containing normally liquid olefins and mixtures of normally liquid olefins, containing substantial amounts of dissolved normally gaseous olefins. We may also employ olefins obtained by the cracking of paraffin wax or by the dehalogenation of alkyl halides, particularly long chain alkyl halides.

The polymers referred to above may be those obtained by polymerizing olefinic hydrocarbons in the presence of catalysts such as sulfuric acid, phosphoric acid, or aluminum chloride, zinc chloride, boron fluoride and other catalysts of the Frledel-Crafts type. For example, we may employ the polymers resulting from thetreatment of monoolefins preferably isomonoolefins such as isobutylene and isoamylene and/or the copolymers obtained by the polymerization of hydrocarbon mixtures containing low molecular weight isoolefins and normal olefins, preferably those of less than six carbon atoms.

We may also employ as the starting material the polymer or synthetic lubricating oil obtained by polymerizing unsaturated hydrocarbons resulting from the vapor phase cracking of parafiin waxes in the presence of aluminum chloride which is fully described in United States Patents Nos.

1,995,260, 1,970,002 and 2,091,398. Still another type oi olefin polymer which may be employed is the polymer resulting from the treatment of vapor phase cracked gasoline and/or gasoline fractions desired, subsequent to the neutralization step by treating with SzClz, PCla, or the like.

The desired product, whether the hydrocarbon chlorosulfonic acid reaction product, the metal with sulfuric acid or solid absorbents such as 6 salt of the reaction product or the neutralized fuller's earth whereby unsaturated polymerized reaction product, may be used in lubricating oils, hydrocarbons are removed. alone or in combination with other well-known Any of the above-mentioned hydrocarbons may lubricant additives, in amounts from about 0.05 be reacted with chlomsulfonlc acid to produce a. per cent to about 10 per cent. Usually an useful lubricating oil addition agent. However, 10 amount of from 0.1 per cent to about 3 per cent it has been found that a greater improvement gives highly favorable results. in the characteristics of the lubricating oil is As specific embodiments of our invention, the attainable when the hydrocarbon-chlorosulfonic following examples are given by way of illusacid reaction product is neutralized with basic tration and are not intended as a limitation of compounds such as the hydroxides, oxides, carthe invention. bonates or bicarbonates of a metal, to form the ExAurLs I fizzf egg gi si g g g i gg i zf igf i An isobutylene polymer having a Saybolt vissr i Ca Co Sn, A1, Zn Cr, Fe, etc, derivatives cosity at 210 F. of 1200 sec. was treated with of the reaction product. Other basic reagents excess of CISOJH wlth stirring at room temper may, be used such as, for example ammonia, or ature. The, product was stirred with excess km or and substituted ammonia such as aminm alcoholic KOH until the color (reddish-purple) The hydrocarbon-chlorosultonic acid reaction had disappeared' The neutralized product was product may be treated with a Sulfur and/01. extracted with hexane and the hexane removed phosphonis-containing com und such as S2C12, on the steam bath SCls, P235, P283, P481, P481, PCls, PCls, P205, and 11 the like. However, it is equally possible to react the hydrocarbon with such compounds before A portion of the product from Example I, betreating the hydrocarbon with the chlorosulfonic fore neutralization, was treated with excess acid. When treating with the sulfur-containing S201: and warmed on the steam bath to remove and/or phosphorus-containing compound, a suitunreacted S2C12. The product was then neuable catalyst such as sulfur or a Friedel-Crafts tralized as in Example 1. catalyst may be used, if desired. The metal salt The eifect of small amounts of the above prodof the hydrocarbon-chlorosulfonic acid reaction nets on lubricating oils is determined by heatproduct may be treated with such, SClz, PCls, 3 ing 250 cc. of the oil containing the desired PC15 and the like, if desired. amount of the addition agent at 330 F.-332 F.

The reaction of the hydrocarbon or the sulin a 500 cc. glass beaker in the presence of 5 furized and/or phosphorized hydrocarbon with square inches of copper and 10 square inches oi. the chlorosulfonic acid may be carried out at iron. Four lass rods of 6 mm. diameter are temperatures oi. from about F. to about 40 suspended in the oil which is stirred at about 150 F. by merely adding from about 5% to about 1300 R. P. M. with a glass stirrer having a 40 50%, preferably about l0%25%, by weight of degree blade pitch. At stated intervals, oil samthe chlorosulfonic acid to the hydrocarbon or ples are taken and sludge, acidity and viscosity sulfurized and/or phosphorized hydrocarbon, and values determined. The glass rods are also instirring the mixture from a few minutes to sevspected for evidence of varnish formation eral hours. The reaction may be carried out in thereon. Varnish values are based on a visual solvents characterized by being substantially nonrating in which a glass rod free of any varnish reactive with chlorosulfonic acids. Typical solis given a rating of 10, while a badly coated rod vents are cyclohexane, light normal hydrocaris given a rating of 1. Rods havin appearances bons, chlorinated hydrocarbons and the like. between these extremes are given intermediate The chlorosulfonic acid reaction product, values. The following data were obtained in whether previously treated with the sulfurized the above described test:

Table in Sludge (mg/10 g. oil) Add? :53- KOH/K- Varnish rating Oil crease 48 hrs.

Mhrs. 48l1rs. 72 hrs. 241m. 48 hrs. 72 hi3. 241m. 48hrs. 722m.

1 Control oil I l,l58 am 915 9.9 16.6 4-5 1 2 Control oil-{4% product of Example I. 285 9 103 377 1.0 5.4 7.9 l0 9 6 3 Control oil+l% product of Example II 298 48 171 379 2.3 5.5 11.2 l0 l0 l0 l Saybolt Universal viscosity at 100 F.

and phosphorized compound or not, may be neutralized by merely stirring with an excess of a metal hydroxide such as KOH, a metal oxide or a metal carbonate in water or alcoholic solution at approximately room temperature. If desired, a solid neutralization agent can be used at more elevated temperatures within the approximate range of from 100 F. to 400 F.

If the neutralized product has not already been treated with the sulfurizing and/or phos- Rating scale l0==no deposit, 1: very heavy deposit.

The above data show the superiority of Examples I and II over the high grade control oil.

While we have described the use of our additives in lubricating oils, our invention is not limited to such use, since these reaction products may be employed in other petroleum products such as white oils, greases, waxes and the like, to increase the resistance thereof to oxidation and sludging. to inhibit the tendency thereof to corrode metals, and to deactivate metal surfaces which the above phorizing agent, this step may be carried out. if 76 products may contact.

While we have described our invention with reference to particular embodiments thereof, other modifications may be made without departing from the scope and spirit of the invention. We do not wish to limit our invention to the examples set forth except in so far as the same is defined by the following claims.

We claim:

1. A lubricant comprising a lubricating oil normally susceptible to the formation of carbon,

sludge, or varnish during use and an amount sufficient to reduce such formation of a product of the type Obtained by the process comprising reacting a, hydrocarbon in separate steps with chlorosulfonic acid and at least one agent selected from the group consisting of a sulfurizing agent, a phosphorizing agent, and a sulfurizing and phos.. phorizing agent and treating with a neutralizing agent subsequent to the reaction step with the chlorosulfonic acid.

2. A lubricant as claimed in claim 1 wherein the hydrocarbon is an olefin polymer.

3. A lubricant comprising a lubricating oil and from about 0.05% to about 10.0% of a product of the type obtained by the process comprising reacting a hydrocarbon in separate steps with chlorosulfonic acid, and at least one agent selected from the group consisting of a sulfurizing agent, a phosphorizing agent, and a sulfurizing and phosphorizing agent and treating with a neutralizing agent subsequent to the reaction step with the chlorosulfonic acid.

4. A lubricant comprising a lubricating oil normally susceptible to the formation of carbon, sludge or varnish during use and an amount suflicient to reduce such formation of a product of the type obtained by the process comprising reacting a hydrocarbon in separate steps with chlorosulfonic acid and a sulfurizing agent, and treating with a'neutralizing agent subsequent to the reaction step with the chlorosulfonic acid.

7. A lubricant comprising a lubricating oil normally susceptible to the formation of carbon, sludge or varnish during use and an amount suincient to reduce such formation of a product of the type obtained by the process comprising reacting a. hydrocarbon in separate steps with chlorosulfonic acid and a sulfurizing and phosphorizing agent, and treating with a neutralizing agent subsequent to the reaction step with the ehlorosulfonic acid.

8. A lubricant comprising a lubricating oil normally susceptible to the formation of carbon, sludge or varnish during use and an amount sufficient to reduce such formation of a product of the type obtained by the process comprising reacting a hydrocarbon in separate steps with chlorosulfonic acid and a sulfurizing agent and treating the product with a neutralizing agent.

9. A lubricant comprising a lubricating oil normally susceptible to the formation of carbon, sludge or varnish during use and an amount sufficient to reduce such formation of a product of the type obtained by the process comprising reacting a hydrocarbon in separate steps with chlorosulfonic acid and a phosphorizing agent, and treating the product with a neutralizing agent.

10, A lubricant comprising a lubricating oil normally susceptible to the formation of carbon, sludge or varnish during use and an amount sufiicient to reduce such formation of a product of the type obtained by the process comprising reacting a hydrocarbon in separate steps with chlorosulfonic acid, a sulfurizing agent and a.

' phosphorizing agent, and treating the product 5. A lubricant comprising a lubricating oil normally susceptible to the formation of carbon, sludge or varnish during use and an amount sufficient to reduce such formation of a product of the type obtained by the process comprising reacting a hydrocarbon in separate steps with chlorosulfonic acid and a phosphorizing agent, and treating with a neutralizing agent subsequent to the reaction step with the chlorosulfonic acid.

6. A lubricant comprising a lubricating oil normally susceptible to the formation of carbon, sludge or varnish during use and an amount sufflcient to reduce such formation of a product of the type obtained by the process comprising reacting a hydrocarbon in separate steps with chlorosulfonic acid, a sulfurizing agent and a phosphorizing agent, and treating with a neutralizing agent subsequent to the reaction step with the chlorosulfonic acid.

with a neutralizing agent.

11. A lubricant comprising a lubricating oil normally susceptible to the formation of carbon, sludge or varnish during use and an amount sumcient to reduce such formation of a product of the type obtained by the process comprising reacting a hydrocarbon in separate steps with chlorosulfonic acid, a sulfurizing and phosphorizing agent, and treating the product with a neutralizing agent.

12. A lubricant comprising a lubricating oil and from about 0.05% to about 10.0% of a. product of the type obtained by the process comprising reacting a hydrocarbon in separate steps with chlorosulfonic acid and a sulfurizing agent and treating with a neutralizing agent subsequent to the reaction step with the chlorosulfonic acid.

13. A lubricant comprising a lubricating oil and from about 0.05% to about 10.0% of a product of the type obtained by the process comprising reacting a hydrocarbon in separate steps with chlorosulfonic acid and a phosphorizing agent, and treating with a neutralizing agent subsequent to the reaction step with the chlorosulfonic acid.

LAWSONW. MIXON; CLARENCE M. LOANE. 

